KR102047267B1 - Epoxy resin, curable resin composition, cured product thereof, and printed circuit board - Google Patents

Abstract

으로 표시되는 2량체(x2)와,
하기 구조식(2)

으로 표시되는 3관능 화합물(x3)과,
하기 구조식(3)

으로 표시되는 4관능 화합물(x4)을 필수의 성분으로서 함유하며, 이들의 합계의 함유율이, GPC 측정에 있어서의 면적 비율로 65% 이상인 것을 특징으로 한다.Cured resin composition exhibits low thermal expansion properties in the cured product, and exhibits low thermal expansion properties, a cured product, and a printed wiring board excellent in low thermal expansion properties due to the small change in heat resistance after thermal history, and an epoxy resin providing such performance. To provide. As an epoxy resin obtained by polyglycidyl etherification of a reaction product of orthocresol, β-naphthol compound, and formaldehyde,
Structural Formula (1)

A dimer (x2) represented by
Structural Formula (2)

Trifunctional compound (x3) represented by
Structural Formula (3)

It is characterized by containing the tetrafunctional compound (x4) represented as an essential component, and the content rate of these sum total is 65% or more by the area ratio in GPC measurement.

Description

Epoxy resin, curable resin composition, the hardened | cured material, and the printed wiring board {EPOXY RESIN, CURABLE RESIN COMPOSITION, CURED PRODUCT THEREOF, AND PRINTED CIRCUIT BOARD}

The present invention has a small change in heat resistance after the thermal history of the cured product to be obtained, is excellent in low thermal expansion properties, and can be suitably used in printed wiring boards, semiconductor encapsulants, paints, mold applications and the like, and these It relates to a curable resin composition having its performance, a cured product thereof, and a printed wiring board.

Epoxy resins are used in adhesives, molding materials, paints, photoresist materials, developing materials, and the like. In addition, epoxy resins have excellent heat resistance and moisture resistance. It is used widely.

Among these various applications, in the field of printed wiring boards, with the trend of miniaturization and high performance of electronic devices, the tendency of high density due to narrowing of the wiring pitch of semiconductor devices is remarkable. As a result, a flip chip connection system for bonding a semiconductor device and a substrate is widely used. In this flip chip connection system, since the solder ball is disposed between the wiring board and the semiconductor, the semiconductor mounting method is a so-called reflow method in which the whole is heated and melt-bonded, so that the wiring board itself is exposed to a high temperature environment during solder reflow. Due to thermal contraction of the wiring board, large stresses may be generated in the solder balls connecting the wiring board and the semiconductor, thereby causing poor connection of the wiring. Therefore, the material of low thermal expansion coefficient is calculated | required for the insulating material used for a printed wiring board.

In addition, high-melting-point solders that do not use lead have become mainstream due to legal regulations on environmental problems in recent years, and the reflow temperature is increasing. In connection with this, the connection defect resulting from the curvature of the printed wiring board by the heat resistance change of the insulating material at the time of reflow is also becoming serious. In other words, a material having a small change in physical properties during reflow is required.

In order to meet these demands, for example, a thermosetting resin composition based on a naphthol novolac epoxy resin obtained by reacting naphthol, formaldehyde and epichlorohydrin is proposed as a solution to technical problems such as low thermal expansion. (See patent document 1 below).

However, the naphthol novolak-type epoxy resin has an improved effect of improving the coefficient of thermal expansion of the cured product to be obtained because of the rigidity of the skeleton compared with the general phenol novolak-type epoxy resin, but it is not sufficient to satisfy the recently required level. Moreover, since the heat resistance of the hardened | cured material changes large with thermal history, the heat resistance change after reflow is large in a printed wiring board use, and it was easy to produce the connection defect of said printed wiring board.

JP 62-20206

Accordingly, the problem to be solved by the present invention is that the cured resin composition exhibits low heat expansion after heat history in the cured product, and has a low heat expandability because the curable resin composition exhibiting low thermal expansion properties, the cured product and heat resistance change after heat history are small. It is providing the printed wiring board and the epoxy resin which provides such a performance.

MEANS TO SOLVE THE PROBLEM In order to solve the said subject, as a result of earnestly examining, as an epoxy resin which polyglycidyl-ether-reacted the reaction product of orthocresol, (beta) -naphthol compound, and formaldehyde, the dimer of (beta) -naphthol compound, And an epoxy resin containing a trifunctional compound and a tetrafunctional compound having a specific structure in a predetermined ratio, exhibit excellent low thermal expansion properties in the cured product, and increase the reactivity of the epoxy resin itself, resulting in a change in heat resistance after the thermal history. It has been found that the number is reduced and the present invention has been completed.

That is, the present invention is an epoxy resin obtained by polyglycidyl etherification of a reaction product of an orthocresol, a β-naphthol compound, and formaldehyde,

Structural Formula (1)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

A dimer (x2) represented by

Structural Formula (2)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

Trifunctional compound (x3) represented by

Structural Formula (3)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

The tetrafunctional compound (x4) represented by the above is contained as an essential component, and the content rate of these sum total is 65% or more by area ratio in GPC measurement, It is related with the epoxy resin characterized by the above-mentioned.

The present invention further relates to a curable resin composition comprising the above epoxy resin and a curing agent as essential components.

This invention relates also to the hardened | cured material formed by making the said curable resin composition harden-react.

This invention also relates to the printed wiring board obtained by impregnating the resin composition which mix | blended and varnished the organic composition with the said curable resin composition to a reinforcing base material, and laminating | stacking and crimping copper foil.

According to the present invention, a cured resin composition exhibiting low thermal expansion in the cured product, and a curable resin composition exhibiting low thermal expansion properties, a cured product, and a printed wiring board excellent in low thermal expansion due to a small change in heat resistance after thermal history, such a The epoxy resin which gives performance can be provided.

1 is a GPC chart of a cresol-naphthol resin (a-1) obtained in Example 1. FIG.
2 is a GPC chart of an epoxy resin (A-1) obtained in Example 1. FIG.
3 is a C ¹³ NMR chart of the epoxy resin (A-1) obtained in Example 1. FIG.
4 is an MS spectrum of the epoxy resin (A-1) obtained in Example 1. FIG.
5 is a GPC chart of an epoxy resin (A-2) obtained in Example 2. FIG.
6 is a GPC chart of an epoxy resin (A-3) obtained in Example 3. FIG.
7 is a GPC chart of an epoxy resin (A′-1) obtained in Comparative Synthesis Example 1. FIG.

Hereinafter, the present invention will be described in detail.

The epoxy resin of the present invention is an epoxy resin obtained by polyglycidyl etherification of a reaction product of orthocresol, β-naphthol compound, and formaldehyde,

Structural Formula (1)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

A dimer (x2) represented by

Structural Formula (2)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

Trifunctional compound (x3) represented by

Structural Formula (3)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)

It contains tetrafunctional compound (x4) represented as an essential component, and the content rate of these sum total is 65% or more by the area ratio in GPC measurement.

That is, the epoxy resin of this invention is a polyglycidyl ether of the polycondensate which uses an orthocresol, (beta) -naphthol compound, and formaldehyde as a raw material, and is a mixture containing the thing of various resin structures, The said dimer (x2), the trifunctional compound (x3) and the tetrafunctional compound (x4) are contained in a high concentration of 65% or more in total.

Among these, the tetrafunctional compound (x4) has a high content of glycidyl group and a very high reactivity of the glycidyl group itself. The effect of suppressing the change in heat resistance due to this becomes even more remarkable.

In addition, since the trifunctional compound (x3) or the tetrafunctional compound (x4) has a cresol skeleton in its molecular structure, it has excellent solvent solubility and shows an effect of easily adjusting the varnish, but the cresol skeleton itself has an orientation property. Since it falls, the hardened | cured material does not become excellent in low thermal expansion property. In this invention, the said dimer (x2) is used together with the said trifunctional compound (x3) and the said tetrafunctional compound (x4), and the content rate of these sum totals 65% or more by area ratio by GPC. By adjusting to the range, the outstanding low thermal expansion property can be expressed, without sacrificing the ease of varnish adjustment at all. Thus, this invention utilizes the characteristic that the solvent solubility of the said trifunctional compound (x3) or the said tetrafunctional compound (x4) is excellent, and a varnish adjustment is easy, and the said dimer (inherently high molecular orientation property is difficult to adjust a varnish) While using y), varnish adjustment is easy, and it has the characteristic that the outstanding low thermal expansion property can be expressed.

In the epoxy resin of this invention, the content rate of the sum total of the said dimer (x2), the said trifunctional compound (x3), and the said tetrafunctional compound (x4) is 65% by the area ratio in GPC measurement as mentioned above. As mentioned above, when it is less than 65%, since the effect of the said molecular orientation property and the effect excellent in reactivity are not fully exhibited, it becomes a hardened | cured material with a large thermal expansion coefficient and the heat resistance change after a thermal history. Especially, since hardened | cured material with a smaller thermal expansion coefficient and a change in heat resistance after thermal history is obtained, the content rate of the sum total of the said dimer (x2), the said trifunctional compound (x3), and the said tetrafunctional compound (x4) is 70% or more. It is more preferable.

Moreover, since the content rate of the said dimer (x2) in the epoxy resin of this invention is excellent in solvent solubility, and the hardened | cured material excellent in low thermal expansion property is obtained, it is 5 to 40% of range in the area ratio in GPC measurement. It is preferable that it is and it is more preferable that it is 10 to 30% of range.

Since the content rate of the said trifunctional compound (x3) in the epoxy resin of this invention is excellent in low thermal expansion property, and the hardened | cured material which changes also the heat resistance after heat history is obtained, it is 25 to 70% by the area ratio in GPC measurement. It is preferable that it is the range of, and it is more preferable that it is 35 to 60% of range.

Since the content rate of the said tetrafunctional compound (x4) in the epoxy resin of this invention is a hardened | cured material with small heat resistance change after heat history, it is preferable that it is 10 to 40% of range in area ratio in GPC measurement, It is more preferable that it is 10 to 30% of range.

The epoxy of this invention calculated by GPC measurement by the following conditions is content rate in the epoxy resin of the said dimer (x2), the said trifunctional compound (x3), and the said tetrafunctional compound (x4) in this invention. It is the ratio of the peak area of each said structure with respect to the total peak area of resin.

<GPC measurement condition>

Measuring apparatus: "HLC-8220 GPC" manufactured by Tosoh Corp.

Column: Guard column "HXL-L" made by Tosoh Corp.

`` TSK-GEL G2000HXL '' made by + Toso Corporation

`` TSK-GEL G2000HXL '' made by + Toso Corporation

`` TSK-GEL G3000HXL '' made by + Toso Corporation

`` TSK-GEL G4000HXL '' made by + Toso Corporation

Detector: RI (differential refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corp.

Measurement condition: column temperature 40 ℃

Developing solvent tetrahydrofuran

Flow rate 1.0ml / min

Standard: Based on the measurement manual of "GPC-8020 Model II version 4.10", the following monodisperse polystyrene having a known molecular weight was used.

(Use Polystyrene)

"A-500" made by Toso Corporation

"A-1000" made by Toso Corporation

"A-2500" made by Toso Corporation

"A-5000" made by Toso Corporation

"F-1" made by Toso Corporation

"F-2" made by Toso Corporation

"F-4" made by Toso Corporation

"F-10" made by Toso Corporation

"F-20" made by Toso Corporation

"F-40" made by Toso Corporation

"F-80" made by Toso Corporation

"F-128" made by Toso Corporation

Sample: The 1.0 mass% tetrahydrofuran solution was filtered with the micro filter in conversion of resin solid content (50 microliters).

In the structural formula (1) representing the dimer (x2), R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms, and G Is a glycidyl group. Such dimer (x2) is specifically, following structural formula (1-1)-(1-6)

The compound represented by these is mentioned. Among them, in particular, those represented by the structural formula (1-1), that is, R ¹ and R ² in the structural formula (1) are both hydrogen atoms, in that the coefficient of thermal expansion in the cured product becomes small. desirable.

In the structural formula (2) representing the trifunctional compound (x3) of the present invention, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms G is a glycidyl group. Such a functional compound (x3) is specifically, following structural formula (2-1)-(2-6)

The compound represented by these is mentioned. Among them, in particular, those represented by the structural formula (2-1), that is, R ¹ and R ² in the structural formula (2) are both hydrogen atoms, in that the coefficient of thermal expansion in the cured product becomes small. desirable.

In the structural formula (3) representing the tetrafunctional compound (x4) of the present invention, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, and an alkoxy group having 1 to 4 carbon atoms G is a glycidyl group. Such tetrafunctional compound (x4) is specifically the following structural formula (3-1)-(3-6)

The compound represented by these is mentioned. Among them, in particular, those represented by the structural formula (3-1), that is, R ¹ and R ² in the structural formula (3) are both hydrogen atoms, in that the coefficient of thermal expansion in the cured product becomes small. desirable.

The epoxy resin of this invention has the following structural formula (4) other than the said dimer (x2), the said trifunctional compound (x3), and the said tetrafunctional compound (x4).

(In formula, R <^1> and R <^2> respectively independently represents a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxy group, G represents a glycidyl group, n represents a repeating unit Is an integer greater than or equal to 3)

In n may contain another polyfunctional compound of 3 or more. When the epoxy resin of this invention contains another polyfunctional compound whose n is 3 or more in the said Formula (4), hardening of this invention that the expansion rate in hardened | cured material and the heat resistance change after heat history can be reduced more Since it fully exhibits, the content rate of the sum total of the said dimer (x2), the said trifunctional compound (x3), and the said tetrafunctional compound (x4) is 65% or more by area ratio in GPC measurement, and the said dimer ( In x2), the said trifunctional compound (x3), the said tetrafunctional compound (x4), and the said polyfunctional compound (X), it is preferable that the content rate of the sum total of the compound whose n is 3-5 is 85% or more.

It is preferable that the softening point of the epoxy resin of this invention is the range of 70-100 degreeC from the point which is excellent in the solvent solubility of the epoxy resin itself, and is especially 75-90 from the point which can highly combine low thermal expansion property and solvent solubility. It is preferable that it is the range of ° C.

Moreover, it is preferable that the epoxy equivalent of this invention is the epoxy equivalent of the range of 220-300 g / eq from the point which the low thermal expansion property of hardened | cured material becomes favorable.

It is preferable that the epoxy resin of this invention has the value of the molecular weight distribution (Mw / Mn) in the range of 1.00-1.50 since the heat resistance change after heat history becomes small. In addition, in this invention, molecular weight distribution (Mw / Mn) is from the value of the weight average molecular weight (Mw) measured on the conditions similar to GPC measurement conditions at the time of obtaining the content rate of said each component, and the number average molecular weight (Mn). It is a calculated value.

The epoxy resin of this invention described in detail above can be manufactured by the following method 1 or method 2, for example.

Method 1: β-naphthol compound and formaldehyde were reacted in the presence of an organic solvent and an alkali catalyst, and then reacted by addition of orthocresol in the presence of formaldehyde to obtain a cresol-naphthol resin (step 1), Next, epihalohydrin is made to react with the obtained cresol-naphthol resin (process 2), and the target epoxy resin is obtained.

Method 2: In the presence of an organic solvent and an alkali catalyst, orthocresol, the β-naphthol compound, and formaldehyde were reacted to obtain a cresol-naphthol resin (step 1), and then to the obtained cresol-naphthol resin epihalohi A method of obtaining the target epoxy resin by reacting aspirin (step 2).

In this invention, in the process 1 of the said method 1 or 2, the said trifunctional compound (x3) and said 2 are used by using an alkali catalyst as a reaction catalyst and using less organic solvent with respect to a raw material component. The abundance ratio in the epoxy resin of a monomer (x2) can be adjusted to a predetermined range.

As an alkali catalyst used here, inorganic alkalis, such as alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, a metal sodium, metal lithium, sodium hydride, sodium carbonate, potassium carbonate, etc. are mentioned, for example. It is preferable that the usage-amount is a range which becomes 0.01-2.0 times with respect to the total number of phenolic hydroxyl groups of the ortho cresol which is a raw material component, and the (beta) -naphthol compound.

Moreover, methyl cellosolve, isopropyl alcohol, ethyl cellosolve, toluene, xylene, methyl isobutyl ketone etc. are mentioned as an organic solvent. Among these, especially isopropyl alcohol is preferable at the point which a comparatively high polycondensate has high molecular weight. The use amount of the organic solvent in the present invention is in the range of 5 to 70 parts by mass per 100 parts by mass of the total mass of the orthocresol and the β-naphthol compound as the raw material components, the trifunctional compound (x3) and the dimer (x2). It is preferable at the point which is easy to adjust the existence ratio in the epoxy resin of ()) to a predetermined range.

In the present invention, orthocresol is used as an essential raw material component. Among the cresols, the tetrafunctional compound (x4) and the trifunctional compound (x3) can be efficiently obtained by using an ortho body, and the low thermal expansion properties of the cured product of the obtained epoxy resin are improved.

(Beta) -naphthol compound which is another essential component of this invention is a compound which nuclear-substituted the beta-naphthol and the alkoxy group, such as alkyl groups, such as a methyl group, an ethyl group, a propyl group, t-butyl group, a methoxy group, an ethoxy group, etc. Can be mentioned. Among these, (beta) -naphthol which does not have a substituent is preferable at the point that the heat resistance change after the heat history in the hardened | cured material of the epoxy resin finally obtained becomes few.

In addition, the formaldehyde used here may be a formalin solution which is a state of aqueous solution, and may be paraformaldehyde which is a solid state.

The use ratio of orthocresol and the (beta) -naphthol compound in the process 1 of the said method 1 or the method 2 becomes a molar ratio (orthocresol / (beta) -naphthol compound) [1 / 0.5]-[1/8] It is preferable that adjustment of each component ratio in the epoxy resin finally obtained as being a range is easy.

The reaction input ratio of formaldehyde is a ratio in which formaldehyde is 0.6-2.0 times on a molar basis with respect to the total number of moles of orthocresol and β-naphthol compound, in particular, 0.6-1.5 in terms of excellent low thermal expansion properties. It is preferable that it is a ratio used as a multiple.

In step 1 of the method 1, a predetermined amount of β-naphthol compound, formaldehyde, an organic solvent, and an alkali catalyst are added to the reaction vessel, and reacted at 40 to 100 ° C. After completion of the reaction, orthocresol (if necessary Therefore, formaldehyde) can be further added and reacted under the temperature condition of 40-100 degreeC, and the target polycondensate can be obtained.

After completion | finish of reaction of process 1, after completion | finish of reaction, neutralization or water washing process is performed until the pH value of a reaction mixture becomes 4-7. What is necessary is just to perform neutralization treatment and water washing treatment in accordance with a conventional method, For example, acidic substances, such as an acetic acid, phosphoric acid, sodium phosphate, can be used as a neutralizing agent. After neutralizing or washing with water, the organic solvent can be distilled off under reduced pressure heating to obtain a target polycondensate.

In step 1 of the method 2, a predetermined amount of β-naphthol compound, orthocresol, formaldehyde, an organic solvent, and an alkali catalyst are added to the reaction vessel, and reacted at 40 to 100 ° C to obtain a target polycondensate. Can be.

After completion | finish of reaction of process 1, after completion | finish of reaction, neutralization or water washing process is performed until the pH value of a reaction mixture becomes 4-7. What is necessary is just to perform neutralization treatment and water washing treatment in accordance with a conventional method, For example, acidic substances, such as an acetic acid, phosphoric acid, sodium phosphate, can be used as a neutralizing agent. After neutralizing or washing with water, the organic solvent can be distilled off under reduced pressure heating to obtain a target polycondensate.

Next, the process 2 of the said method 1 or the method 2 is a process of manufacturing the target epoxy resin by making the polycondensate obtained by the process 1, and epihalohydrin react. Specifically, this step 2 adds epihalohydrin at a rate of 2 to 10 times the amount (based on moles) with respect to the number of moles of phenolic hydroxyl groups in the polycondensate, and further to the number of moles of phenolic hydroxyl groups. The method of making it react for 0.5 to 10 hours at the temperature of 20-120 degreeC, adding 0.9-2.0 times (molar reference | standard) basic catalyst collectively or gradually adding with respect to it. The basic catalyst may be solid or an aqueous solution thereof may be used, and in the case of using an aqueous solution, water and epihalohi are continuously added under reduced pressure or under normal pressure in the reaction mixture while being added continuously. The method may be performed by distilling out the drodine, separating the water to remove water, and epihalohydrin continuously in the reaction mixture.

In the industrial batch, all of the epihalohydrins used for the introduction are new in the initial batch of epoxy resin production, but after the secondary batch, the crude reaction is carried out. It is preferable to use together the epihalohydrins recovered from the product, and the new epihalohydrins corresponding to the ones lost in the minutes consumed in the reaction. The epihalohydrin used at this time is not specifically limited, For example, epichlorohydrin, epibromohydrin, (beta) -methyl epichlorohydrin, etc. are mentioned. Among them, epichlorohydrin is preferable because of industrial availability.

In addition, the basic catalyst may, for example, be an alkaline earth metal hydroxide, an alkali metal carbonate or an alkali metal hydroxide. In particular, alkali metal hydroxides are preferred from the viewpoint of excellent catalytic activity in epoxy resin synthesis reaction, and examples thereof include sodium hydroxide and potassium hydroxide. In use, you may use these basic catalysts in the form of about 10-55 mass% aqueous solution, and may use it in solid form. Moreover, reaction rate in the synthesis | combination of an epoxy resin can be raised by using an organic solvent together. Although it does not specifically limit as such an organic solvent, For example, Alcohol compounds, such as ketones, such as acetone and methyl ethyl ketone, methanol, ethanol, 1-propyl alcohol, isopropyl alcohol, 1-butanol, sec-butanol, tert- butanol , Cellosolves such as methyl cellosolve, ethyl cellosolve, tetrahydrofuran, ether compounds such as 1,4-dioxane, 1,3-dioxane, diethoxyethane, acetonitrile, dimethyl sulfoxide and dimethyl Aprotic polar solvents, such as formamide, etc. are mentioned. These organic solvents may be used independently, respectively, and may use 2 or more types of suitably together in order to adjust polarity.

After washing the reaction product of the epoxidation reaction described above, unreacted epihalohydrin and an organic solvent used in combination are distilled off by distillation under reduced pressure under heating. Furthermore, in order to make an epoxy resin with little hydrolyzable halogen, the obtained epoxy resin is melt | dissolved again in organic solvents, such as toluene, methyl isobutyl ketone, and methyl ethyl ketone, and aqueous solution of alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, is made The reaction may be carried out by addition. At this time, for the purpose of improving the reaction rate, an interphase transfer catalyst such as a quaternary ammonium salt or a crown ether may be present. It is preferable that it is the ratio used as 0.1-3.0 mass parts with respect to 100 mass parts of epoxy resins to be used as the usage-amount when using a phase transfer catalyst. After completion | finish of reaction, the produced | generated salt is removed by filtration, water washing, etc., and also the epoxy resin of the objective of this invention can be obtained by distilling off solvents, such as toluene and methyl isobutyl ketone, under heating and pressure reduction.

Next, the curable resin composition of this invention makes the epoxy resin and hardening | curing agent described in detail above into an essential component.

Examples of the curing agent used herein include amine compounds, amide compounds, acid anhydride compounds, and phenol compounds. Specific examples of the amine compound include diaminodiphenylmethane, diethylenetriamine, triethylenetetramine, diaminodiphenylsulfone, isophoronediamine, imidazole, BF ₃ -amine complex, guanidine derivative, and the like. Examples of the amide compound include diamide diamide, polyamide resin synthesized from dimer of linolenic acid, and ethylene diamine. Examples of the acid anhydride compound include phthalic anhydride, trimellitic anhydride, and pyromelli anhydride. Acid, maleic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylnadic acid, hexahydrophthalic anhydride, methylhexahydrophthalic anhydride, and the like. Examples of the phenolic compound include phenol novolak resins and cresolno. Volac resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, dicyclopentadiene phenol addition type resin, phenol aralkyl resin (xyl Resins), polyhydric hydroxy compounds represented by resorcinol novolac resins and polyhydric phenol novolac resins synthesized from formaldehyde, naphthol aralkyl resins, trimethylol methane resins, tetraphenylolethane resins, naphthol novolacs Resin, naphthol-phenol coaxial novolak resin, naphthol-cresol coaxial novolak resin, biphenyl-modified phenol resin (polyhydric phenol compound in which phenol nucleus is linked to bismethylene group), biphenyl-modified naphthol resin (polyvalent linking phenol nucleus with bismethylene group Naphthol compounds), aminotriazine-modified phenol resins (polyhydric phenol compounds in which phenol nuclei are linked with melamine, benzoguanamine, etc.) or alkoxy group-containing aromatic ring-modified novolac resins (polyhydric linkages in which formaldehyde phenol nucleus and alkoxy group-containing aromatic rings are linked) Polyhydric phenol compounds, such as a phenol compound), etc. are mentioned.

Among these, it is especially preferable to contain many aromatic skeleton in molecular structure from the point of low thermal expansion, specifically, a phenol novolak resin, cresol novolak resin, aromatic hydrocarbon formaldehyde resin modified phenol resin, phenol aralkyl resin, Resorcinol novolak resin, naphthol aralkyl resin, naphthol novolak resin, naphthol-phenol coaxial novolak resin, naphthol-cresol coaxial novolak resin, biphenyl modified phenol resin, biphenyl modified naphthol resin, aminotriazine modified phenolic resin And an alkoxy group-containing aromatic ring-modified novolak resin (a polyhydric phenol compound in which a formaldehyde phenol nucleus and an alkoxy group-containing aromatic ring are linked) are preferable because they are excellent in low thermal expansion.

Although it does not restrict | limit especially as a compounding quantity of the epoxy resin and hardening | curing agent in curable resin composition of this invention, The active group in a hardening | curing agent is 0.7-1.5 with respect to 1 equivalent of the epoxy groups of an epoxy resin in terms of favorable hardened | cured material characteristic obtained. The amount which becomes equivalent is preferable.

Moreover, the hardening accelerator can also be used suitably together in curable resin composition of this invention as needed. Although various things can be used as said hardening accelerator, For example, a phosphorus compound, tertiary amine, imidazole, an organic acid metal salt, Lewis acid, an amine complex salt, etc. are mentioned. Particularly, when used as a semiconductor encapsulation material, it is excellent in curability, heat resistance, electrical properties, moisture resistance, and the like. Thus, triphenylphosphine is used for phosphorus compounds and 1,8-diazabicyclo- [5.4.0 for tertiary amines; ] -Undecene (DBU) is preferred.

In curable resin composition of this invention, although the epoxy resin of this invention mentioned above may be used independently as an epoxy resin component, you may use another epoxy resin in the range which does not impair the effect of this invention. Specifically, other epoxy resins can be used in combination within the range of 30% by mass or more, preferably 40% by mass or more of the epoxy resin of the present invention with respect to the total mass of the epoxy resin component.

As another epoxy resin which can be used together with the said epoxy resin here, various epoxy resin can be used, For example, a bisphenol-A epoxy resin, a bisphenol F-type epoxy resin, a biphenyl type epoxy resin, a tetramethyl biphenyl type Epoxy resin, phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin , Phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin, naphthol aralkyl type epoxy resin, naphthol-phenol coaxial novolak type epoxy resin, aromatic hydrocarbon formaldehyde resin modified phenol resin type epoxy resin, biphenyl novolak type epoxy resin, etc. Can be mentioned.

Among these, phenol aralkyl type epoxy resins, biphenyl novolak type epoxy resins, naphthol novolak type epoxy resins containing a naphthalene skeleton, naphthol aralkyl type epoxy resins, naphthol-phenol coaxial novolak type epoxy resins, and crystalline biphenyls Epoxy resins, tetramethylbiphenyl epoxy resins, xanthene epoxy resins and alkoxy group-containing aromatic ring-modified novolac epoxy resins (compounds in which formaldehyde glycidyl group-containing aromatic rings and alkoxy group-containing aromatic rings are connected) It is especially preferable at the point which the hardened | cured material excellent in heat resistance is obtained.

Curable resin composition of this invention described in detail above is characterized by expressing excellent solvent solubility, and can mix | blend the organic solvent other than each said component. As said organic solvent which can be used here, methyl ethyl ketone, acetone, dimethylformamide, methyl isobutyl ketone, methoxy propanol, cyclohexanone, methyl cellosolve, ethyl diglycol acetate, propylene glycol monomethyl ether acetate, etc. Although the selection and proper usage amount can be suitably selected according to a use, For example, in a printed wiring board use, it is preferable that it is a polar solvent whose boiling point, such as methyl ethyl ketone, acetone, dimethylformamide, is 160 degrees C or less, Moreover, it is preferable to use in the ratio used as 40 to 80 mass% of non volatile matters. On the other hand, in the adhesive film use for buildup, for example, ketones such as acetone, methyl ethyl ketone, cyclohexanone, ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate It is preferable to use acetic acid esters, cellosolves, carbitols such as butyl carbitol, aromatic hydrocarbons such as toluene, xylene, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, and the like. Moreover, it is preferable to use in the ratio used as 30 to 60 mass% of non volatile matters.

In addition, in order to exhibit flame retardance, the said curable resin composition may mix | blend the non-halogen-type flame retardant which does not contain a halogen atom substantially in the range which does not reduce reliability in the field of a printed wiring board, for example.

Examples of the non-halogen flame retardants include phosphorus flame retardants, nitrogen flame retardants, silicone flame retardants, inorganic flame retardants, and organometallic salt flame retardants, and the like, and they may be used alone or in any way. Two or more flame retardants of the same type may be used, or may be used in combination with other flame retardants.

As said phosphorus flame retardant, both an inorganic type and an organic type can be used. Examples of the inorganic compound include inorganic nitrogen-containing phosphorus compounds such as ammonium phosphates such as red phosphorus, ammonium phosphate, diammonium phosphate, triammonium phosphate and ammonium polyphosphate, and amide phosphate. Can be.

Moreover, it is preferable that the said red phosphorus is surface-treated in order to prevent hydrolysis, etc., As a surface treatment method, it is (i) magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, oxidation, for example. Coating treatment with inorganic compounds such as bismuth, bismuth hydroxide, bismuth nitrate or mixtures thereof, (ii) inorganic compounds such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, and mixtures of thermosetting resins such as phenol resins. The method of coating | coating treatment, (i) The method of double coating | covering with thermosetting resins, such as a phenol resin, on the film of inorganic compounds, such as magnesium hydroxide, aluminum hydroxide, zinc hydroxide, titanium hydroxide, etc. are mentioned.

Examples of the organophosphorus compound include 9,10-dihydro, in addition to general-purpose organophosphorus compounds such as phosphate ester compounds, phosphonic acid compounds, phosphinic acid compounds, phosphine oxide compounds, phosphoran compounds and organic nitrogen-containing phosphorus compounds. -9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2,5-dihydrooxyphenyl) -10H-9-oxa-10-phosphaphenanthrene-10-oxide, 10- (2 Cyclic organic phosphorus compounds, such as (7-dihydrooxy naphthyl) -10H-9-oxa-10-phosphazanthrene-10-oxide, and derivatives which made it react with compounds, such as an epoxy resin and a phenol resin, etc. are mentioned. Can be.

Although the compounding quantity is suitably selected according to the kind of phosphorus flame retardant, components other than curable resin composition, and the desired flame retardance, For example, epoxy resin, a hardening | curing agent, a non-halogen flame retardant, and other fillers, additives, etc. are mix | blended When using red phosphorus as a non-halogen flame retardant among 100 mass parts of curable resin compositions, it is preferable to mix | blend in the range of 0.1-2.0 mass parts, and when using an organophosphorus compound, it mixes in the range of 0.1-10.0 mass parts similarly It is preferable, and it is preferable to mix | blend especially in the range of 0.5-6.0 mass parts.

When the phosphorus-based flame retardant is used, hydrotalcite, magnesium hydroxide, a boron compound, zirconium oxide, black dye, calcium carbonate, zeolite, zinc molybdate, activated carbon, or the like may be used in combination with the phosphorus-based flame retardant.

Examples of the nitrogen-based flame retardant include triazine compounds, cyanuric acid compounds, isocyanuric acid compounds, phenothiazines, and the like, and triazine compounds, cyanuric acid compounds, and isocyanuric acid compounds are preferable. Do.

Examples of the triazine compound include melamine, acetoguanamine, benzoguanamine, melon, melam, succinoguanamine, ethylenedimelamine, polyphosphate melamine, triguanamine and the like, for example (i) Aminotriazine sulfate compounds such as guanyl melamine sulfate, melem sulfate, melam sulfate, and (ii) phenols such as phenol, cresol, xylenol, butylphenol and nonylphenol, melamine, benzoguanamine, acetoguanamine and form Melamines, such as guanamine, and a condensate of formaldehyde, (iii) A mixture of the phenol resins, such as a condensate of said (ii), and a phenol formaldehyde condensate, (iii) said (ii), ( And iii) more modified with tung oil, isomerized linseed oil, and the like.

As a specific example of the said cyanuric acid compound, cyanuric acid, melamine cyanurate, etc. are mentioned, for example.

Although the compounding quantity of the said nitrogen-based flame retardant is suitably selected according to the kind of nitrogen-based flame retardant, components other than curable resin composition, and the degree of desired flame retardancy, For example, an epoxy resin, a hardening | curing agent, a non-halogen-type flame retardant, and other fillers and additives It is preferable to mix | blend in the range of 0.05-10 mass parts in 100 mass parts of curable resin compositions which mix | blended all, etc., and it is preferable to mix | blend especially in the range of 0.1-5 mass parts.

Moreover, when using the said nitrogen type flame retardant, you may use a metal hydroxide, a molybdenum compound, etc. together.

As said silicone flame retardant, if it is an organic compound containing a silicon atom, it can use without a restriction | limiting especially, For example, silicone oil, silicone rubber, a silicone resin etc. are mentioned.

Although the compounding quantity of the said silicone type flame retardant is suitably selected according to the kind of silicone type flame retardant, components other than curable resin composition, and the desired flame retardance, For example, all, such as an epoxy resin, a hardening | curing agent, a non-halogen type flame retardant, and other fillers and additives, etc. It is preferable to mix | blend in 0.05-20 mass parts in 100 mass parts of curable resin compositions which mix | blended this. Moreover, when using the said silicone type flame retardant, you may use together a molybdenum compound, an alumina, etc.

As said inorganic flame retardant, a metal hydroxide, a metal oxide, a metal carbonate compound, a metal powder, a boron compound, low melting glass, etc. are mentioned, for example.

As a specific example of the said metal hydroxide, aluminum hydroxide, magnesium hydroxide, dolomite, hydrotalcite, calcium hydroxide, barium hydroxide, zirconium hydroxide, etc. are mentioned, for example.

Specific examples of the metal oxides include zinc molybdate, molybdenum trioxide, zinc stannate, tin oxide, aluminum oxide, iron oxide, titanium oxide, manganese oxide, zirconium oxide, zinc oxide, molybdenum oxide, cobalt oxide, bismuth oxide, Chromium oxide, nickel oxide, copper oxide, tungsten oxide and the like.

As a specific example of the said metal carbonate compound, zinc carbonate, magnesium carbonate, calcium carbonate, barium carbonate, basic magnesium carbonate, aluminum carbonate, iron carbonate, cobalt carbonate, titanium carbonate, etc. are mentioned, for example.

As a specific example of the said metal powder, aluminum, iron, titanium, manganese, zinc, molybdenum, cobalt, bismuth, chromium, nickel, copper, tungsten, tin, etc. are mentioned, for example.

As a specific example of the said boron compound, zinc borate, zinc metaborate, barium metaborate, a boric acid, borax etc. are mentioned, for example.

Specific examples of the low-melting glass, for example, Schiff Li (beam kuseuyi, brown Co.), hydrated glass _{SiO 2 -MgO-H 2 O,} PbO-B 2 O 3 based, ZnO-P ₂ O ₅ -MgO-based , P ₂ O ₅ -B ₂ O ₃ -PbO-MgO system, P-Sn-OF system, PbO-V ₂ O ₅ -TeO ₂ system, Al ₂ O ₃ -H ₂ O system, lead borosilicate Can be mentioned.

The amount of the inorganic flame retardant is appropriately selected depending on the type of the inorganic flame retardant, components other than the curable resin composition, and the degree of desired flame retardancy. For example, all of epoxy resins, curing agents, non-halogen flame retardants, and other fillers and additives, etc. It is preferable to mix | blend in the range of 0.05-20 mass parts in 100 mass parts of curable resin compositions which mix | blended the compound, and it is preferable to mix | blend especially in the range of 0.5-15 mass parts.

As said organometallic salt flame retardant, for example, a ferrocene, an acetylacetonato metal complex, an organometallic carbonyl compound, an organo cobalt salt compound, an organo sulfonic acid metal salt, a metal atom and an aromatic compound or a heterocyclic compound are ion-bonded or coordinated-bonded. Compounds and the like.

Although the compounding quantity of the said organometallic salt type flame retardant is suitably selected according to the kind of organometal salt type flame retardant, components other than curable resin composition, and desired flame retardancy, For example, an epoxy resin, a hardening | curing agent, a non-halogen type flame retardant, and other fillers It is preferable to mix | blend in 0.005-10 mass parts in 100 mass parts of curable resin compositions which mix | blended all, and additives.

An inorganic filler can be mix | blended with curable resin composition of this invention as needed. As said inorganic filler, fused silica, crystalline silica, alumina, silicon nitride, aluminum hydroxide etc. are mentioned, for example. When especially compounding quantity of the said inorganic filler is made large, it is preferable to use fused silica. The fused silica may be any of crushed and spherical forms, but in order to increase the blending amount of the fused silica and to suppress an increase in the melt viscosity of the molding material, it is preferable to use a spherical silica mainly. Moreover, in order to raise the compounding quantity of spherical silica, it is preferable to adjust the particle size distribution of spherical silica suitably. The filling rate is preferably higher in consideration of flame retardancy, and particularly preferably 20% by mass or more based on the total amount of the curable resin composition. Moreover, when using for uses, such as an electrically conductive paste, electrically conductive fillers, such as silver powder and copper powder, can be used.

The curable resin composition of this invention can add various compounding agents, such as a silane coupling agent, a mold release agent, a pigment, and an emulsifier as needed.

Curable resin composition of this invention is obtained by mixing each said component uniformly. The curable resin composition of this invention which the epoxy resin of this invention, the hardening | curing agent, and the hardening accelerator further mix | blended as needed can be easily made into hardened | cured material by the method similar to the method known conventionally. As said hardened | cured material, shaping | molded hardened | cured material, such as a laminated body, a casting object, an adhesive layer, a coating film, and a film, is mentioned.

Examples of applications in which the curable resin composition of the present invention is used include printed wiring board materials, resin mold materials, adhesives, interlayer insulating materials for buildup substrates, adhesive films for buildup, and the like. Moreover, among these various uses, in the insulating material for printed wiring boards, an electronic circuit board, and the adhesive film for buildup, what is called electron which embedded passive components, such as a capacitor, and active components, such as an IC chip, in a board | substrate. It can be used as an insulating material for component embedded substrates. Among these, it is preferable to use it for a printed wiring board material and an adhesive film for buildup from the characteristics, such as low thermal expansion property and solvent solubility, whose change of heat resistance after heat history is small.

Here, in order to manufacture a printed circuit board from the curable resin composition of this invention, the method of impregnating the varnish-like curable resin composition containing the said organic solvent in a reinforcement base material, and laminating | stacking and copper foil is mentioned. As a reinforcing base material which can be used here, paper, a glass cloth, a glass nonwoven fabric, an aramid paper, an aramid cloth, a glass mat, a glass rubbing cloth, etc. are mentioned. When this method is described in more detail, first, the above-mentioned curable resin composition of the varnish phase is heated at the heating temperature according to the solvent species used, Preferably it is 50-170 degreeC, and the prepreg which is hardened | cured material is obtained. Although it does not specifically limit as mass ratio of the resin composition and reinforcement base material used at this time, Usually, it is preferable to prepare so that resin powder in a prepreg may be set to 20-60 mass%. Next, the prepreg obtained as mentioned above is laminated | stacked by the conventional method, and it heat-compresses by overlapping red copper foil and heat-pressing at 170-250 degreeC for 10 minutes-3 hours under 1-10 Mpa pressure. The target printed circuit board can be obtained.

When using curable resin composition of this invention as a resist ink, after using a cationic polymerization catalyst as a hardening | curing agent of the said curable resin composition, and further adding a pigment, talc, and a filler, it is set as the composition for resist inks, After apply | coating on a printed board by the screen printing system, the method of making a resist ink hardened | cured material is mentioned.

When using curable resin composition of this invention as a electrically conductive paste, the method of disperse | distributing fine electroconductive particle in the said curable resin composition to make the composition for anisotropic conductive films, the paste resin composition for circuit connection and anisotropic conductivity liquid at room temperature, for example. The method of making it into an adhesive agent is mentioned.

As a method of obtaining the interlayer insulation material for buildup board | substrates from curable resin composition of this invention, the curable resin composition which mix | blended rubber, a filler, etc. suitably was spray-coated and the curtain coating method to the wiring board which formed the circuit, for example. After apply | coating using etc., it hardens. Thereafter, if necessary, after drilling a predetermined through-hole portion or the like, it is treated with a roughening agent, and the surface is washed with water to form unevenness to form a metal such as copper. Is plated. As said plating method, electroless plating and electrolytic plating process are preferable, and an oxidizing agent, an alkali, an organic solvent etc. are mentioned as said roughening agent. By repeating these operations sequentially as desired, a buildup substrate can be obtained by alternately building up and forming a resin insulating layer and a conductor layer of a predetermined circuit pattern. However, the through hole portion is drilled after formation of the resin insulating layer of the outermost layer. Moreover, the copper foil with resin which semi-hardened the said resin composition on copper foil was heated and crimped at 170-250 degreeC on the wiring board in which the circuit was formed, and a roughening surface is formed and the process of a plating process is abbreviate | omitted and a buildup is carried out. It is also possible to manufacture a substrate.

The method of manufacturing the adhesive film for buildup from the curable resin composition of this invention applies the curable resin composition of this invention on a support film, for example, forms a resin composition layer, and makes it the adhesive film for multilayer printed wiring boards. Can be mentioned.

When the curable resin composition of this invention is used for the adhesive film for buildups, the said adhesive film softens on the temperature conditions (typically 70 degreeC-140 degreeC) of the laminate in a vacuum laminating method, and simultaneously with the lamination of a circuit board, It is important to exhibit fluidity (resin flow) in which the resin filling in the via hole or through hole existing in the substrate is possible, and it is preferable to blend each of the above components to express such characteristics.

Here, the diameter of the through hole of the multilayer printed wiring board is usually 0.1 to 0.5 mm, and the depth is usually 0.1 to 1.2 mm, and it is usually preferable to enable resin filling in this range. In addition, when laminating both surfaces of a circuit board, it is preferable to fill about 1/2 of a through hole.

Specifically, in the method for producing the adhesive film, after the curable resin composition of the varnish phase of the present invention is prepared, the varnish phase composition is applied to the surface of the support film (Y), and the heating or hot air spraying or the like is performed. It can manufacture by drying the organic solvent and forming the layer (X) of curable resin composition.

The thickness of the layer X formed is made into the thickness of a conductor layer normally. Since the thickness of the conductor layer which a circuit board has is normally 5-70 micrometers, it is preferable that the thickness of a resin composition layer has a thickness of 10-100 micrometers.

Moreover, the layer (X) in this invention may be protected by the protective film mentioned later. By protecting with a protective film, adhesion | attachment and a scratch of dust etc. to the surface of a resin composition layer can be prevented.

Said support film and protective film are polyolefins, such as polyethylene, a polypropylene, and polyvinyl chloride, polyethylene terephthalate (it may abbreviate as "PET" hereafter), polyester, such as polyethylene naphthalate, poly Carbonate, a polyimide, metal foil, such as a release paper, copper foil, aluminum foil, etc. are mentioned. Moreover, the support film and the protective film may perform the mold release process other than a mud process and a corona treatment.

Although the thickness of a support film is not specifically limited, Usually, it is 10-150 micrometers, Preferably it is used in the range of 25-50 micrometers. Moreover, it is preferable that the thickness of a protective film shall be 1-40 micrometers.

The supporting film Y is peeled off after lamination to the circuit board or after forming an insulating layer by heat curing. When peeling of the support film Y after heat-hardening an adhesive film, adhesion | attachment of dust etc. in a hardening process can be prevented. When peeling after hardening, a release process is normally given to a support film beforehand.

Next, the method of manufacturing a multilayer printed wiring board using the adhesive film obtained as mentioned above is, for example, when layer (X) is protected by the protective film, after peeling these, layer (X) is removed. It laminates on one or both surfaces of a circuit board by the vacuum lamination method so that it may directly contact a circuit board, for example. The method of lamination may be batch type or continuous by a roll. In addition, before performing lamination, you may heat (pre-heat) an adhesive film and a circuit board as needed.

Condition of the laminate is preferably a contact bonding temperature (lamination temperature) 70~140 ℃, preferably ^{1~11kgf / ㎠ (9.8 × 10 4} ~107.9 × 10 4 N / ㎡) the contact pressure to, and the air pressure 20 It is preferable to laminate under reduced pressure of mmHg (26.7 hPa) or less.

As a method of obtaining the hardened | cured material of this invention, what is necessary is just to conform to the hardening method of general curable resin composition, For example, heating temperature conditions may be suitably selected according to the kind, use, etc. of the hardening | curing agent to combine, but obtained by the said method What is necessary is just to heat a composition in the temperature range of about 20-250 degreeC.

Therefore, by using the said epoxy resin, the solvent solubility of an epoxy resin improves remarkably, and when it is set as the hardened | cured material, there is little change in the heat resistance after thermal history, and a low thermal expansion coefficient can be expressed, and it is a state-of-the-art printed wiring board material Applicable Moreover, the said epoxy resin can be manufactured easily and efficiently by the manufacturing method of this invention, and the molecular design corresponding to the level of the above-mentioned performance made into the objective becomes possible.

EXAMPLE

Next, although an Example and a comparative example demonstrate this invention concretely, "part" and "%" are mass references | standards unless there is particular notice below. In addition, the softening point, GPC, NMR, and MS spectrum were measured on condition of the following.

1) Softening point measurement method: JIS K7234

2) GPC: Measurement conditions are as follows

Measuring apparatus: "HLC-8220 GPC" manufactured by Tosoh Corp.

Column: Guard column "HXL-L" made by Tosoh Corp.

`` TSK-GEL G2000HXL '' made by + Toso Corporation

`` TSK-GEL G2000HXL '' made by + Toso Corporation

`` TSK-GEL G3000HXL '' made by + Toso Corporation

`` TSK-GEL G4000HXL '' made by + Toso Corporation

Detector: RI (Differential Refractometer)

Data processing: "GPC-8020 Model II Version 4.10" manufactured by Tosoh Corp.

Measurement condition: column temperature 40 ℃

Developing solvent tetrahydrofuran

Flow rate 1.0ml / min

Standard: The following monodisperse polystyrene whose molecular weight was known based on the measurement manual of "GPC-8020 Model II version 4.10" was used.

(Use Polystyrene)

"A-500" made by Toso Corporation

"A-1000" made by Toso Corporation

"A-2500" made by Toso Corporation

"A-5000" made by Toso Corporation

"F-1" made by Toso Corporation

"F-2" made by Toso Corporation

"F-4" made by Toso Corporation

"F-10" made by Toso Corporation

"F-20" made by Toso Corporation

"F-40" made by Toso Corporation

"F-80" made by Toso Corporation

"F-128" made by Toso Corporation

Sample: The 1.0 mass% tetrahydrofuran solution was filtered with the micro filter in conversion of resin solid content (50 microliters).

3) ¹³ C-NMR: Measurement conditions are as follows.

Device: Nihon Denshi Co., Ltd. "JNM-ECA500"

Measurement mode: SGNNE (1H full decoupling method of NOE cancellation)

Solvent: Dimethyl sulfoxide

Pulse angle: 45 ° pulse

Sample concentration: 30wt%

Number of integrations: 10000 times

4) MS: JMS-T100GC manufactured by Nippon Denshi Corporation

Example 1

216 parts by mass of beta -naphthol (1.5 moles), 250 parts by mass of isopropyl alcohol, 122 parts by mass of aqueous solution of formalin 122 parts by mass (1.50 moles), 49% to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a sorting tube, and a stirrer. 31 mass parts (0.38 mol) of sodium hydroxides were added, it heated up, stirring from room temperature to 75 degreeC, and stirred at 75 degreeC for 1 hour. Next, 81 parts by mass (0.75 mol) of orthocresol was added thereto, and the mixture was further stirred at 75 ° C. for 8 hours. After completion | finish of reaction, after adding 45 mass parts of monobasic sodium phosphates and neutralizing, 630 mass parts of methyl isobutyl ketones were added, and wash | cleaning was repeated 3 times with 158 mass parts of water, and it dried under heat_reduction | reduced_pressure, and cresol-naphthol resin (a- 1) 290 mass parts was obtained. The GPC chart of the obtained cresol-naphthol resin (a-1) is shown in FIG. The hydroxyl equivalent of cresol-naphthol resin (a-1) was 140 grams / equivalent, and the content rate of the trifunctional compound represented by the following structural formula (a) calculated from the GPC chart was 51.5%.

Next, 140 mass parts (1.0 equivalent of hydroxyl group) and epichlorohydrin 463 mass parts of cresol-naphthol resin (a-1) obtained by the said reaction, carrying out nitrogen gas purge to the flask with a thermometer, a cooling tube, and the stirrer 5.0 mol) and 53 mass parts of n-butanols were melt | dissolved under input stirring. After heating up at 50 degreeC, 220 mass parts (1.10 mol) of 20% aqueous sodium hydroxide aqueous solution were added in 3 hours, and it was made to react at 50 degreeC further for 1 hour after that. After completion | finish of reaction, stirring was stopped, the water layer gathered in the lower layer was removed, stirring was restarted, and unreacted epichlorohydrin was distilled off under 150 degreeC pressure reduction. 300 mass parts of methyl isobutyl ketones and 50 mass parts of n-butanol were added and dissolved in the crude epoxy resin obtained by it. Furthermore, 15 mass parts of 10 mass% sodium hydroxide aqueous solution was added to this solution, and it was made to react at 80 degreeC for 2 hours, and water washing was repeated 3 times with 100 mass parts of water until pH of a washing | cleaning liquid became neutral. Next, the inside of the system was dehydrated by azeotropy and after filtration, the solvent was distilled off under reduced pressure to obtain 192 parts by mass of the target epoxy resin (A-1). The GPC chart of the obtained epoxy resin (A-1) is shown in FIG. 2, an NMR chart, and FIG. 3, and an MS spectrum is shown in FIG. The epoxy equivalent of epoxy resin (A-1) was 227 grams / equivalent, the softening point was 78 degreeC, and molecular weight distribution (Mw / Mn) was 1.25. The content of the component corresponding to the dimer (x2) calculated from the GPC chart is 16.1%, the content of the component corresponding to the trifunctional compound (x3) represented by the following structural formula (b) is 42.0%, and the tetrafunctional compound. The content rate of components corresponded to (x4) was 19.7%, and their total was 77.8%. In addition, in the said dimer (x2), the said trifunctional compound (x3), the said tetrafunctional compound (x4), and the said polyfunctional compound (X), the content rate of the sum total of the compound whose n is any of 3-5 is 91.4. Was%. From the MS spectrum, a peak of 588 representing the trifunctional compound represented by the following structural formula (b) was detected.

Example 2

188 mass parts of epoxy resins (A-2) were obtained like Example 1 except having changed into 107 mass parts (1.32 mol) of 37% formalin aqueous solution, and 61 mass parts (0.56 mol) of orthocresol. The GPC chart of the obtained epoxy resin (A-2) is shown in FIG. The epoxy equivalent of epoxy resin (A-2) was 232 grams / equivalent, the softening point was 76 degreeC, and molecular weight distribution (Mw / Mn) was 1.32. The content of the component corresponding to the dimer (x2) calculated from the GPC chart is 27.4%, the content of the component corresponding to the trifunctional compound (x3) represented by the following structural formula (b) is 35.4%, and the tetrafunctional compound. The content rate of components corresponded to (x4) was 14.6%, and their total was 77.4%. In addition, in the said dimer (x2), the said trifunctional compound (x3), the said tetrafunctional compound (x4), and the said polyfunctional compound (X), the content rate of the sum total of the compound whose n is any one of 3-5 is 90.5. Was%.

Example 3

190 mass parts of epoxy resins (A-3) were obtained like Example 1 except having changed into 152 mass parts (1.87 mol) of 37% formalin aqueous solution, and 122 mass parts (1.13 mol) of orthocresol. The GPC chart of the obtained epoxy resin (A-3) is shown in FIG. Epoxy equivalent of the epoxy resin (A-3) was 226 grams / equivalent, the softening point was 87 degreeC, and molecular weight distribution (Mw / Mn) was 1.24. The content of the component corresponding to the dimer (x2) calculated from the GPC chart is 6.0%, the content of the component corresponding to the trifunctional compound (x3) represented by the following structural formula (b) is 27.9%, and the tetrafunctional compound. The content rate of the component corresponded to (x4) was 31.7%, and the sum total was 65.6%. In addition, in the said dimer (x2), the said trifunctional compound (x3), the said tetrafunctional compound (x4), and the said polyfunctional compound (X), the content rate of the sum total of the compound whose n is any one of 3-5 is 87.6. Was%.

Comparative Synthesis Example 1

505 parts by mass of α-naphthol (3.50 mol), 158 parts by mass of water, and 5 parts by mass of oxalic acid were added to a flask equipped with a thermometer, a dropping funnel, a cooling tube, a sorting tube, and a stirrer, and the temperature was raised from room temperature to 100 ° C. for 45 minutes. Stirring while stirring. Subsequently, 177 mass parts (2.45 mol) of 42 mass% formalin aqueous solution was dripped for 1 hour. After completion of dropping, the mixture was further stirred at 100 ° C for 1 hour, and then heated up to 180 ° C for 3 hours. After the completion of reaction, the water remaining in the reaction system was removed under heating and reduced pressure to obtain 498 parts by mass of naphthol resin (a'-1). The hydroxyl equivalent of the obtained naphthol resin (a'-1) was 154 grams / equivalent.

Next, 154 mass parts (1.0 equivalent of hydroxyl group) of the naphthol resin (a'-1) obtained by the said reaction was carried out similarly to Example 1, carrying out nitrogen gas purge to the flask with a thermometer, a cooling tube, and the stirrer, and an epoxy resin. 202 parts by mass of (A'-1) were obtained. The GPC chart of the obtained epoxy resin (A'-1) is shown in FIG. The epoxy equivalent of epoxy resin (A'-1) was 237 grams / equivalent.

Examples 4-6 and Comparative Example 1

According to the mixing | blending of following Table 1, as a hardening | curing agent, TD-2090 (phenol novolak resin, hydroxyl equivalent: 105 g / eq) made from DIC Corporation was used as an epoxy resin (A-1), (A-2), 2-ethyl-4-methylimidazole (2E4MZ) is blended with (A-3) or (A'-1) as a curing accelerator so that the non-volatile content (NV) of each composition is 58% by mass. Methyl ethyl ketone was mixed and adjusted. Next, the laminated sheet was started by curing under the following conditions, and the thermal expansion coefficient and physical property change were evaluated by the following method. The results are shown in Table 1.

<Laminated Plate Manufacturing Conditions>

Materials: Glass cloth "# 2116" made by Nitto Boseki Corporation (210 x 280 mm)

Ply number: 6

Prepregization condition: 160 ℃

Curing conditions: 200 ℃, 1.5 hours at 40㎏ / ㎠, plate thickness after molding: 0.8mm

<Heat resistance change due to thermal history (change amount of heat resistance: ΔTg): DMA (Tg difference between first measurement and second measurement)>

Using a viscoelasticity measuring device (DMA: solid viscoelasticity measuring device "RSAII" manufactured by Leo Matrix, Rectangular tensioning method; frequency 1 Hz, heating rate 3 ° C / min), the change in elastic modulus is maximum twice under the following temperature conditions The temperature (Tg) which becomes (the largest rate of change of tan-delta) was measured.

Temperature conditions

First measurement: temperature rise at 3 ° C./min from 35 ° C. to 275 ° C.

2nd measurement: Temperature rise to 3 degree-C / min from 35 degreeC to 330 degreeC

The temperature difference obtained respectively was evaluated as (DELTA) Tg.

<Coefficient of thermal expansion>

The laminated board was cut out to the size of 5 mm x 5 mm x 0.8 mm, and it was made into a test piece, and the thermomechanical analysis was performed in compression mode using the thermomechanical analyzer (TMA: SS-6100 by Seiko Instruments).

Measuring conditions

Measuring load: 88.8mN

Temperature rise rate: 2 times at 10 ° C / min

Measuring temperature range: -50 ℃ to 300 ℃

The measurement on the said conditions was performed twice with respect to the same sample, and the average linear expansion coefficient in the temperature range of 40 degreeC-60 degreeC in the 2nd measurement was evaluated as a thermal expansion coefficient.

TABLE 1

The symbol in Table 1 is as follows.

TD-2090: phenol novolak type phenolic resin ("TD-2090" made by DIC Corporation, hydroxyl equivalent: 105 g / eq)

2E4MZ: Curing accelerator (2-ethyl-4-methylimidazole)

Claims (11)

As an epoxy resin obtained by polyglycidyl etherification of a reaction product of orthocresol, β-naphthol compound, and formaldehyde,
Structural Formula (1)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)
A dimer (x2) represented by
Structural Formula (2)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)
Trifunctional compound (x3) represented by
Structural Formula (3)

(Wherein R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, and G represents a glycidyl group)
It contains tetrafunctional compound (x4) represented as an essential component, and the content rate of these sum total is 65% or more by area ratio in GPC measurement, and the content rate of said tetrafunctional compound (x4) is GPC It is 10 to 40% of range in area ratio in a measurement, The epoxy resin characterized by the above-mentioned. The method of claim 1,
Epoxy resin whose epoxy equivalent exists in the range of 220-300 g / eq. The method of claim 1,
Epoxy resin which has a softening point in the range of 70-100 degreeC. The method of claim 1,
Epoxy resin whose value of molecular weight distribution (Mw / Mn) is in the range of 1.00-1.50. Curable resin composition which uses the epoxy resin as described in any one of Claims 1-4, and a hardening | curing agent as an essential component. Hardened | cured material formed by making hardening reaction of the curable resin composition of Claim 5. The method of claim 6,
Hardened | cured material whose Tg difference ((DELTA) Tg) of a 1st measurement and a 2nd measurement is 6 degrees C or less in Tg measured with a viscoelasticity measuring instrument. The printed wiring board obtained by impregnating the resin composition which mix | blended and varnished the organic composition with the curable resin composition of Claim 5 by laminating | stacking a copper foil and heat-compressing. In the presence of an organic solvent and an alkali catalyst, the β-naphthol compound and formaldehyde are reacted under a temperature condition of 40 to 100 ° C., followed by addition of orthocresol in the presence of formaldehyde and reaction under a temperature condition of 40 to 100 ° C. To obtain a cresol-naphthol resin (step 1), and then react epihalohydrin to the obtained cresol-naphthol resin (step 2) to obtain an epoxy resin. In the presence of an organic solvent and an alkali catalyst, orthocresol, β-naphthol compound, and formaldehyde are reacted under a temperature condition of 40 to 100 ° C to obtain a cresol-naphthol resin (step 1), and then, the obtained cresol-naphthol resin Epihalohydrin is made to react (step 2), and an epoxy resin is obtained, The manufacturing method of the epoxy resin characterized by the above-mentioned.
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